Deep-UV (180-280 nm) phosphors have attracted tremendous interest in tri-band-based white light-emitting diode (LED) technology, bio- and photochemistry, as well as various medical fields. However, the application of many UV-emitting materials has been hindered due to their poor thermal or chemical stability, complex synthesis, and environmental harmfulness. A particular concern is posed by the utilization of rare earths affected by rising price and depletion of natural resources. As a consequence, the development of phosphors without rare-earth elements represents an important challenge. In this work, as a potential UV-C phosphor, undoped ZnAl2O4 fibers have been synthesized by a cost-efficient wet chemical route. The rare-earth-free ZnAl2O4 nanofibers exhibit a strong UV emission with two bands peaking at 5.4 eV (230 nm) and 4.75 eV (261 nm). The emission intensity can be controlled by tuning the Zn/Al ratio. A structure-property relationship has been thoroughly studied to understand the origin of the UV emission. For this reason, ZnAl2O4 nanofibers have been analyzed by X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), X-ray diffraction (XRD), and Raman spectroscopy techniques showing that a normal spinel structure of the synthesized material is preserved within a wide range of Zn/Al ratios. The experimental evidence of a strong and narrow band at 7.04 eV in the excitation spectrum of the 5.4 eV emission suggests its excitonic nature. Moreover, the 4.75 eV emission is shown to be related to excitons perturbed by lattice defects, presumably oxygen or cation vacancies. These findings shed light on the design of UV-C emission devices for sterilization based on a rare-earth-free phosphor, providing a feasible alternative to the conventional phosphors doped with rare-earth elements.